(a) Field of the Invention
This invention relates to a method of producing a bead-like glycidyl (meth)acrylate (hereinafter referred to as G(M)A) as well as to a modified bead-like polymer produced from said polymer and to a method of producing the same.
(b) Description of the Prior Art
As the materials for shaping, polymers in the form of pellets, flakes, globules, fine particles, etc. are easy in handling. In some cases, it is convenient to produce particulate polymers from the start. Further, fields of use which require particulate polymers are not few, as latex diagnostic medicines, gels for use in liquid chromatography, lubricants, etc.
Polymers containing epoxy groups can be applied to various fields of use because a variety of functional groups can be introduced into them owing to their reactivity. For example in Japanese Pat. Kokai No. 96261/1982, there is disclosed a technique of producing immunization-active fine particles by reacting G(M)A polymer fine particles with an immunization-active substance having amino groups. According to said patent, it is described that the polymerization is carried out in a solvent which dissolves the monomer but precipitates the resulting polymer, and that by suitably selecting a monomer composition and polymerization medium, a G(M)A polymer in the form of fine particles of 0.03-10.mu. can be obtained. However, in this process, an organic solvent is used as the polymerization medium and in the washing step, etc. so that in conducting the process on an industrial scale, there are many problems to be taken into consideration, such as bad odor, in labor environment and safety. In use in fields such as liquid chromatographic gels, ion-exchange resins, etc., polymers having particle diameters usually from 20 to 1000.mu. are used, and an industrial production method of a globular polymer of such particle diameters is demanded.
In Journ. Chem. Soc. Japan, 1979 (12), pp 1756-1759, there is disclosed a method of producing a globular GMA polymer as a basic material for producing a chelating ion exchange resin. To obtain the globular polymer, large quantities of sodium sulfate and calcium carbonate are used as dispersing agents together with gelatine, and to decompose and remove the calcium carbonate from the resulting polymer, complicated operations are needed such as the addition of hydrochloric acid and washing with hot water.
In recent years, liquid chromatography is utilized not only as an analytical means but also as an industrial separation means in many fields such as food industry, medical products industry, synthesis and purification of chemical products and intermediates, inorganic industry, textile industry, etc. As the gels for use in such liquid chromatography, various gel products are being developed, such as dextran-cross-linked polymer gels, acrylamide-cross-linked polymer gels, cross-linked polystyrene gels, cross-linked polyvinyl acetate gels, cross-linked polyethylene glycol dimethacrylate gels, silanol-polyoxyethylene gels, etc. However, gels of high separation and treating abilities are generally expensive. For example, Cephadex gel (dextran cross-linked polymer gel) produced by Pharmacia Fine Chemical is excellent in performance but is very expensive, so that it is a problem to use it for industrial use in which a large quantity of gel is filled into enormous columns.